Method and apparatus for in situ distillation and hydrogenation of carbonaceous materials

ABSTRACT

A method of distilling and hydrogenating the hydrocarbon content of carbonaceous materials wherein hot hydrogen is introduced into the carbonaceous material in sufficient quantity and at sufficient temperature to concurrently release and distill the hydrocarbon content. Preferred apparatus for practicing the method includes a source of hydrogen, means for varying the temperature of the hydrogen, an underground cavern in the carbonaceous material, and temperature modulating means at the face of the shale for regulating the temperature temperature of the hydrogen.

United States Patent [72] lnventor Clarence 1. Justheim Salt Lake City,Utah [21] Appl. No. 641,089 [22] Filed Apr. 25, 1967 [45] Patented Aug.10, 1971 [73] Assignee Justheim Petroleum Company Salt Lake City, UtahContinuation-impart oi application Ser. No. 550,343, May 16, 1966, nowabandoned.

[54] METHOD AND APPARATUS FOR IN SITU DISTILLATION AND HYDROGENATION OFCARBONACEOUS MATERIALS 17 Claims, 4 Drawing Figs.

[52] US. Cl 166/247, 166/57, 166/64, 166/267, 166/272 [51] Int. Cl E2lb43/24 [50] Field of Search 166/247, 57, 64, 250, 252, 265, 266, 271,267, 272, 302, 274, 303, 308

[56] References Cited UNITED STATES PATENTS 2,595,979 5/1952 Pevere eta1. 166/303 20 HYDROGEN scum? i I I6 l I f v V1 17 4 x 7/ WW 2,857,00210/1958 Pevere et a1. 166/303 2,969,226 1/1961 Huntington 166/261 X3,051,235 8/1962 Banks 1 166/261 3,084,919 4/1963 Slater 166/261 X3,102,588 9/1963 Fisher 166/261 3,237,689 3/1966 Justheim 166/2473,246,697 4/1966 Natland.. 166/57 3,303,881 2/1967 Dixon 166/2473,327,782 6/1967 Hujsak r 166/261 3,342,257 9/1967 Jacobs et a1. 166/247Primary Examiner--Stephen .l. Novosad Attorney-Mallinekrodt &Mallinckrodt ABSTRACT: A method of distilling and hydrogenating thehydrocarbon content of carbonaceous materials wherein hot hydrogen isintroduced into the carbonaceous material in sufficient quantity and atsufficient temperature to concurrently release and distill thehydrocarbon content. Preferred apparatus for practicing the methodincludes a source of hydrogen, means for varying the temperature of thehydrogen, an underground cavern in the carbonaceous material, andtemperature modulating means at the face of the shale for regulating thetemperature temperature of the hydrogen.

PATENTEU AUG] 0 l9?! SHEET 1 0F 2 HYDROGEN SOU/FfiE INVENTOR.

CLARENCE I. JUSTHEIM BY MA/L/NCKPODT 8 MALL/NCKPOD ATTORNEYS ATTORNE Y8METHOD AND APPARATUS FOR IN SITU DISTILLATION AND HYDROGENATION FCARBONACEOUS MATERIALS The present application constitutes acontinuation-in-part of my copending application, Ser. No. 550,343,filed May 16, 1966, which has been abandoned in favor of thisapplication.

BRIEF DESCRIPTION This invention relates to thermal distillation andhydrogenation of the hydrocarbon content of naturally occurring depositsof oil shales and other carbonaceous materials, without first removingthem from their underground locations. It is concerned with both amethod for accomplishing such distillation and hydrogenation and withapparatus for carrying out the method to advantage.

Vast deposits of oil shale, oil-bearing sand, and other carbonaceousmaterials exist in many regions of the world. Little has been done toexploit such deposits for removing their hydrocarbon content, largelybecause of the great expense involved in mining them, in refining them,and in handling the vast quantities of solid waste matter usuallyinvolved. In my U.S. Pat. No. 3,237,689, granted Mar. 1, 1966, Idisclose a method and plant for distilling solid carbonaceous materialsin situ, which involves the controlled application of heat generated,for example, by a nuclear reactor so as to reduce the cost of producingusable hydrocarbon products.

If the heat is transmitted to the in situ deposit of carbonaceousmaterials in the form of hot hydrogen substantially undiluted by othergases l have found that even greater savings can be realized in therecovery of usable oil and gasoline products, since these usefulproducts are effectively and efficiently produced and are recovereddirectly from the formation, without significant expense involved infurther processing recovered vapors.

My method is useful wherever deposits of oil-bearing shale or othercarbonaceous materials are found and, in contradistinction to otherprocesses employing hydrogen for mild hydrogenation, is highlyefficient, since substantially pure hydrogen is used to both carry theheat and to hydrogenate the kerogen almost instantaneously as it isreleased in response to application of the heat. Excess hydrogen that isnot consumed in removing oxygen, nitrogen, and sulfur from the kerogenis recycled and is reused.

The hot hydrogen can be from any source, but preferably will be obtainedfrom a nuclear reactor utilizing hydrogen as a coolant or fromcarbonization of coal. However, the hydrogen can be produced and heatedin any conventional commercial manner. Naturally, in the handling of thehydrogen, customary safety precautions must be taken to prevent itsbeing combined with oxygen and inadvertently ignited.

There is shown in the accompanying drawings a specific embodiment of theinvention representing what is presently regarded as the best mode ofcarrying out the generic concepts in actual practice. From the detaileddescription of this presently preferred form of the invention, othermore specific objects and features will become apparent.

THE DRAWINGS In the drawings:

FIG. I is a somewhat schematic top plan view showing a typicalstructural arrangement of novel apparatus for carrying out the methodofthe invention;

FIG. 2, a top plan view of a typical bore hole arrangement according tothe invention, drawn to a smaller scale than the other views;

FIG. 3, a vertical section taken on the line 3-3 of FIG. I; and

FIG. 4, a horizontal section taken on the line 4-4 of FIG. 3.

DETAILED DESCRIPTION Referring now to the drawings:

In the illustrated preferred embodiment, the apparatus of the inventionincludes a suitable source of hydrogen, as indicated, feeding throughpipe 11 to a heat exchanger 12 and thence through a pipe 13, anddistribution pipes 14 (FIGS 3 and 4) to a cavern 15 that surrounds anunderground room 16. An access hole 17 extends from the ground surface18 to the room 16 and provides a convenient throughway for the pipe 13.

The source of hydrogen can be a nuclear reactor from which hydrogencoolant is discharged at very hot temperature, or the hydrogen can beproduced by carbonization of coal either in situ, or after it has beenmined, it being known that when heated to between l,2001,500 F.practically all coals evolve large quantities of hydrogen. In theseinstances it will be desirable, at least initially, to cool the hydrogento a working temperature of about 800 F. for oil shale and within therange of about 200 to about 500 F. for oil-bearing sands by means of theheat exchanger. However, any other commercial means of producinghydrogen can be employed, with heat being supplied by means of the heatexchanger if necessary.

In practicing the method of the invention, and as a safety measure, itis preferred that valve 19 in line 11 be operated to first admit arelatively inert and inexpensive gas such as carbon dioxide or nitrogenfrom a source of purging gas 20 into line 11 and through the entiresystem. After the system has been purged, the valve 19 can be eithermanually or automatically manipulated to cut off the purging gas and toadmit hydrogen into line 11.

As the hydrogen is passed through the heat exchanger 12 its temperatureis modulated, if required, in a manner to be further explained, and pump21 forces it through lines 13 and 14 and into the cavern 15. Should thepressure in the system increase above that desired, relief valve 22 willopen to allow flow of hydrogen through line 23 to a recycle conduit 24.

The hot hydrogen in cavern 15 acts directly on the face 25 of thedeposit of carbonaceous material, and, as the heat releases hydrocarbonsfrom the deposit, the hydrogen reacts therewith to separatecontaminating oxygen, sulfur, and nitrogen from the useful hydrocarbons.

The temperature of the hydrogen at the face of the deposit is regulatedby a thermostat 26, i.e. any suitable temperature control means, placedadjacent to the face. The thermostat is electrically connected tocontrol valves 27 and 28, and, in response to signals of the thermostatthe controls are regulated to supply hot or cold fluid through jacket 29(FIG. I) of the heat exchanger. Thus, the temperature of the hydrogen ismodulated as it passes through jacket 29 in accordance with the signaltransmitted by the thermostat 26.

If, for example, the hydrogen is too hot when it reaches the face of thematerial being treated, flow through valve 28 to the heat exchanger willbe increased in proportion to flow through valve 28 to the heatexchanger will be increased in proportion to flow through valve 27, tothereby decrease the temperature of control fluid in jacket 29.Similarly, if the temperature of the hydrogen at the face 24 is toocold, then flow through valve 27 will be increased proportionate to thatthrough valve 28 to increase the temperature ofthe water in jacket 29.Obviously, any commercially available heat exchange system capable ofmodulating the temperature of the hydrogen passing through pipe 11 couldas well be used.

The thermostat will be set to maintain the temperature of the hydrogenat the deposit face at least high enough to insure distillation of thehydrocarbon content of the deposit. For oil shales this will be about800 F. and for bituminous tar sands about 2()0-500 IQ, for example.

As the hydrocarbons are released in response to the heat application andare acted on by the hydrogen the resulting reaction vapors are forced uprecovery holes 30, that terminate in cavern [5, to condenser 31. Becausethe bituminous material has some natural cracks and fissures in it someof the hot hydrogen is forced therein, and the vapors released andtreated are forced up recovery holes 32 spaced away from the cavern. Thecracks and fissures may increase as the hydrocarbon material is removed,apparently due to a settling of the material. lf desired, the porosityof the material can be increased in preparation for treating inaccordance with the invention. Thus, for example, explosives can be usedin the fracturing process. Also, the temperature of the hydrogen can beincreased as required to cause fracturing. For oil shale material, thishas been found to be at least 2,000 F., but not so high that fusion ofthe shale results. The fusion temperature is readily determined bylaboratory tests on the material being treated. When this amount of heatis applied, it has been found that fissures are formed in the shale thatextend ahead of the advancing thermal front. These fissures then providechannels in which the hot hydrogen can travel to more efficientlydistill and hydrogenate the material being treated.

The spacing and number of recovery holes 30 and 32 will be in accordancewith good design practices and will depend on the characteristics of thedeposit being treated, the volume of hydrogen available and theequipment available for use.

Collector pipes 34 carry the vapors from the recovery holes 30 and 32 tothe condenser 31.

The recovered vapors are passed into condenser 31 and useful hydrocarbonproducts are condensed and discharged through line 35. The gases arethen separated at 36 and the unconsumed hydrogen is recycled throughline 24 back to line 11, from where it can again be used in thedistillation and hydrogenation process. The remaining gases aredischarged through line 37 and can be used to operate a steam electricgenerating plant that will then generate the electrical energy necessaryto operate the pumps and auxiliary equipment of the system in the mannerdisclosed in my US. Pat. No. 3,237,689. If desired, these gases couldalso be used for other purposes.

Door 38, through the insulated wall 39 of room 16, allows access byworkmen to cavern l and the face of the carbonaceous material. Thus, thethermostat can be readily repositioned on the face as found desirable,and, if desired, it can be inserted in a plugged bore hole in the mannerdisclosed in my aforementioned US. Pat. No. 3,237,689.

it is within the scope of the invention that very high temperatures canbe used to crack and fissure an area of shale surrounding the caverninto which the hot hydrogen is supplied and thereafter the temperaturemay be reduced to permit efficient distillation ofthe hydrocarboncontent.

Since during the release of hydrocarbons, hydrogen is also released fromthe carbonaceous bearing material, it is also within the scope of theinvention that once the process is underway the released hydrogen iscollected and cycled along with that from the illustrated hydrogensource, thus reducing the amount of hydrogen required from theillustrated source.

Whereas this invention is here described and illustrated with respect toa certain form thereof, it is to be understood that many variations arepossible.

I claim:

1. A method of distilling and hydrogenating the hydrocarbon content of adeposit of carbonaceous material in situ, which comprises the steps ofintroducing into such a carbonaceous material substantially purehydrogen at a temperature high enough to crack and fissure an area ofthe carbonaceous material beyond the point of introduction of saidhydrogen;

thereafter regulating the temperature of the hydrogen to continue itsintroduction into the carbonaceous material at a lower temperaturesufficient to release the hydrocarbon content of the material as avapor; and

recovering fluid products produced by reaction of the hydrogen withheat-released hydrocarbon vapors.

2. Apparatus for distilling and hydrogenating the carbonaceous contentof carlmnaceous materials, in situ, comprising a source ol'suhstnntlallypure hydrogen;

an underground cavern in which humans can work formed in a deposit ofmaterial to be treated;

means for transporting the hydrogen from the source to the face of thedeposit defining the cavern;

means for modulating the temperature of said hydrogen to maintain thehydrogen at the face at a desired temperature for distillation of thecarbonaceous materials; and

means for recovering distilled and hydrogenated products resulting fromthe application of said hydrogen to said face ofthe deposit.

3. Apparatus for distilling and hydrogenating the carbonaceous contentof carbonaceous materials, in situ, comprising a source of substantiallypure hydrogen;

an underground cavern formed in a deposit of material to be treated;

means for transporting the hydrogen from the source to the face of thedeposit defining the cavern;

a heat exchanger through which the hydrogen is passed for modulating thetemperature of said hydrogen to maintain it at the face of the depositat a desired temperature for distillation of the carbonaceous material;

a thermostat at the face of the deposit;

means for changing the effect of said heat exchanger on the hydrogenpassed therethrough in response to the temperature sensed by thethermostat; and

means for recovering distilled and hydrogenated products resulting fromthe application of said hydrogen to said face of the deposit.

4. Apparatus according to claim 3, further including an insulated roomin the cavern;

an access hole extending from the ground surface to the room; and

an access door allowing individual movement from within said room to theface of the deposit.

5. Apparatus according to claim 3, further including means for supplyingpurging gas through the means for transporting hydrogen from the sourceto the face of the deposit prior to the supplying of hydrogentherethrough.

6. Apparatus according to claim 3, further including means for recyclingunconsumed hydrogen recovered with the distilled and hydrogenatedproducts.

7. A method of distilling and hydrogenating the hydrocarbon content of adeposit of carbonaceous material in situ, which comprises the steps ofpurging the carbonaceous material by the introduction thereinto of aninert gas;

introducing into the purged carbonaceous material substantially purehydrogen at a temperature adapted to release the hydrocarbon content ofthe material as a vapor; and

recovering fluid products produced by reaction of the hydrogen withheat-released hydrocarbon vapors.

8. A method of distilling and hydrogenating the hydrocarbon content of adeposit of oil shale in situ, which comprises the steps of applyingsubstantially pure hydrogen to an exposed face of the shale at atemperature sufficient to fissure the shale as the heat front advances,but not high enough to cause fusion of the shale;

introducing into the fissured shale substantially pure hydrogen at atemperature adapted to release the hydrocarbon content thereofas avapor; and

recovering fluid products produced by reaction of the hydrogen withheat-released hydrocarbon vapors.

9. The method of claim 8, wherein the temperature at which the hydrogenis applied is at least 2,000 F.

10 The method of claim 9 wherein the hot hydrogen is supplied by anuclear reactor.

ll. Apparatus for distilling and hydrogenating the carbonaceous contentof carbonaceous materials in situ, comprismg n hcal cxchnngcr;

menus for passing substantially pure hydrogen through said heatexchanger in heat exchange relationship with a thcrmal fluid;

means for introducing the hydrogen into an underground deposit ofcarbonaceous material;

temperature responsive means within said underground deposit;

means for modulating the temperature of the hydrogen for maintaining itat a desired temperature for distillation of the carbonaceous material;and

means for recovering distilled and hydrogenated products resulting fromthe introduction of the hydrogen into the carbonaceous material.

12. A method of distilling and hydrogenating the hydrocarbon content ofa deposit of a carbonaceous material in situ, comprising the steps ofheating substantially pure hydrogen to a temperature sufficient torelease the hydrocarbon content of said carbonaceous material as avapor;

introducing said heated hydrogen into the carbonaceous material in thenatural unheated state of said material; and

recovering fluid products produced by reaction of the hydrogen with theheat-released hydrocarbon vapors.

13. The method of claim 5 wherein hydrogen released from thecarbonaceous material is collected and circulated with the unconsumedhydrogen introduced into the carbonaceous material from a sourceindependent of the said carbonaceous material.

14. The method of claim 5 further including the steps of condensing thevapor products to form useful oil products;

separating extraneous gases from unconsumed hydrogen;

and

recycling the unconsumed hydrogen into the carbonaceous material.

15. The method of claim 5 wherein the temperature of the hydrogen ismodulated prior to introduction in accordance with the releasetemperature of the hydrocarbon vapors.

16. The method of claim 5 wherein hydrogen is introduced in excess ofthe stoichiometric amount necessary to react with the oxygen, nitrogen,and sulfur present in the kerogen.

17. The method of claim 16, wherein the excess hydrogen is recycled incontinued application of the process.

1. A method of distilling and hydrogenating the hydrocarbon content of adeposit of carbonaceous material in situ, which comprises the steps ofintroducing into such a carbonaceous material substantially purehydrogen at a temperature high enough to crack and fissure an area ofthe carbonaceous material beyond the point of introduction of saidhydrogen; thereafter regulating the temperature of the hydrogen tocontinue its introduction into the carbonaceous material at a lowertemperature sufficient to release the hydrocarbon content of thematerial as a vapor; and recovering fluid products produced by reactionof the hydrogen with heat-released hydrocarbon vapors.
 2. Apparatus fordistilling and hydrogenating the carbonaceous content of carbonaceousmaterials, in situ, comprising a source of substantially pure hydrogen;an underground cavern in which humans can work formed in a deposit ofmaterial to be treated; means for transporting the hydrogen from thesource to the face of the deposit defining the cavern; means formodulating the temperature of said hydrogen to maintain the hydrogen atthe face at a desired temperature for distillation of the carbonaceousmaterials; and means for recovering distilled and hydrogenated productsresulting from the application of said hydrogen to said face of thedeposit.
 3. Apparatus for distilling and hydrogenating the carbonaceouscontent of carbonaceous materials, in situ, comprising a source ofsubstantially pure hydrogen; an underground cavern formed in a depositof material to be treated; means for transporting the hydrogen from thesource to the face of the deposit defining the cavern; a heat exchangerthrough which the hydrogen is passed for modulating the temperature ofsaid hydrogen to maintain it at the face of the deposit at a desiredtemperature for distillation of the carbonaceous material; a thermostatat the face of the deposit; means for changing the effect of said heatexchanger on the hydrogen passed therethrough in response to thetemperature sensed by the thermostat; and means for recovering distilledand hydrogenated products resulting from the application of saidhydrogen to said face of the deposit.
 4. Apparatus according to claim 3,further including an insulated room in the cavern; an access holeextending from the ground surface to the room; and an access doorallowing individual movement from within said room to the face of thedeposit.
 5. Apparatus according to claim 3, further including means forsupplying purging gas through the means for transporting hydrogen fromthe source to the face of the deposit prior to the supplying of hydrogentherethrough.
 6. Apparatus according to claim 3, further including meansfor recycling unconsumed hydrogen recovered with the distilled andhydrogenated products.
 7. A method of distilling and hydrogenating thehydrocarbon content of a deposit of carbonaceous material in situ, whichcomprises the steps of purging the carbonaceous material by theintroduction thereinto of an inert gas; introducing into the purgedcarbonaceous material substantially pure hydrogen at a temperatureadapted to release the hydrocarbon content of the material as a vapor;and recovering fluid products produced by reaction of the hydrogen withheat-released hydrocarbon vapors.
 8. A method of distilling andhydrogenating the hydrocarbon content of a deposit of oil shale in situ,which comprises the steps of applying substantially pure hydrogen to anexposed face of the Shale at a temperature sufficient to fissure theshale as the heat front advances, but not high enough to cause fusion ofthe shale; introducing into the fissured shale substantially purehydrogen at a temperature adapted to release the hydrocarbon contentthereof as a vapor; and recovering fluid products produced by reactionof the hydrogen with heat-released hydrocarbon vapors.
 9. The method ofclaim 8, wherein the temperature at which the hydrogen is applied is atleast 2,000* F.
 10. The method of claim 9, wherein the hot hydrogen issupplied by a nuclear reactor.
 11. Apparatus for distilling andhydrogenating the carbonaceous content of carbonaceous materials insitu, comprising a heat exchanger; means for passing substantially purehydrogen through said heat exchanger in heat exchange relationship witha thermal fluid; means for introducing the hydrogen into an undergrounddeposit of carbonaceous material; temperature responsive means withinsaid underground deposit; means for modulating the temperature of thehydrogen for maintaining it at a desired temperature for distillation ofthe carbonaceous material; and means for recovering distilled andhydrogenated products resulting from the introduction of the hydrogeninto the carbonaceous material.
 12. A method of distilling andhydrogenating the hydrocarbon content of a deposit of a carbonaceousmaterial in situ, comprising the steps of heating substantially purehydrogen to a temperature sufficient to release the hydrocarbon contentof said carbonaceous material as a vapor; introducing said heatedhydrogen into the carbonaceous material in the natural unheated state ofsaid material; and recovering fluid products produced by reaction of thehydrogen with the heat-released hydrocarbon vapors.
 13. The method ofclaim 5 wherein hydrogen released from the carbonaceous material iscollected and circulated with the unconsumed hydrogen introduced intothe carbonaceous material from a source independent of the saidcarbonaceous material.
 14. The method of claim 5 further including thesteps of condensing the vapor products to form useful oil products;separating extraneous gases from unconsumed hydrogen; and recycling theunconsumed hydrogen into the carbonaceous material.
 15. The method ofclaim 5 wherein the temperature of the hydrogen is modulated prior tointroduction in accordance with the release temperature of thehydrocarbon vapors.
 16. The method of claim 5 wherein hydrogen isintroduced in excess of the stoichiometric amount necessary to reactwith the oxygen, nitrogen, and sulfur present in the kerogen.
 17. Themethod of claim 16, wherein the excess hydrogen is recycled in continuedapplication of the process.